EP3414092B1 - Matériau d'emballage flexible et son procédé de préparation - Google Patents

Matériau d'emballage flexible et son procédé de préparation Download PDF

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Publication number
EP3414092B1
EP3414092B1 EP16750699.7A EP16750699A EP3414092B1 EP 3414092 B1 EP3414092 B1 EP 3414092B1 EP 16750699 A EP16750699 A EP 16750699A EP 3414092 B1 EP3414092 B1 EP 3414092B1
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Prior art keywords
examples
flexible substrate
polymer
less
ink composition
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EP16750699.7A
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English (en)
French (fr)
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EP3414092A1 (de
Inventor
Asaf Salant
David Idan
Alexander STOLOV
Einat GLICK
Roy LUBINSKI
Chen ZIGDON
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HP Indigo BV
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HP Indigo BV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/08—Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/005—Oriented
    • B29K2995/0053—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/24—Organic non-macromolecular coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
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    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the flexible packaging material serves to protect the product from, for example, moisture, oxidation or pathogens, while also providing information to the user regarding the nature and origin of the product contained therein.
  • Figure 1 shows a schematic of a process for producing a flexible packaging material in accordance with the present disclosure.
  • carrier fluid As used herein, “carrier fluid”, “carrier liquid,” “carrier,” or “carrier vehicle” refers to the fluid in which pigment particles, colorant, charge directors and other additives can be dispersed to form a liquid electrostatic composition or a liquid electrophotographic composition.
  • the carrier liquids may include a mixture of a variety of different agents, such as surfactants, cosolvents, viscosity modifiers, and/or other possible ingredients.
  • electrostatic ink composition or “liquid electrophotographic composition” generally refers to an ink composition that is typically suitable for use in an electrostatic printing process, sometimes termed an electrophotographic printing process. It may comprise pigment particles, which may comprise a thermoplastic resin.
  • pigment generally includes pigment colorants, magnetic particles, aluminas, silicas, and/or other ceramics or organo-metallics, whether or not such particulates impart color.
  • pigment colorants generally includes pigment colorants, magnetic particles, aluminas, silicas, and/or other ceramics or organo-metallics, whether or not such particulates impart color.
  • pigment colorants can be used more generally to describe not only pigment colorants, but other pigments such as organometallics, ferrites, ceramics, etc.
  • copolymer refers to a polymer that is polymerized from at least two monomers.
  • lamination bond strength refers to the force (per length) required to delaminate a laminated material, and is expressed in units of Newton/inch, or N/in.
  • the lamination bond strength can be measured according to standard techniques, in particular ASTM F0904-98R08.
  • the lamination bond strength of a flexible packaging material described herein refers the strength to delaminate the material at the interface between a thermally activatable laminating material and either of the two materials to which the thermally activatable laminating material has bonded.
  • melt flow rate generally refers to the extrusion rate of a resin through an orifice of defined dimensions at a specified temperature and load, usually reported as temperature/load, e.g. 190°C/2.16 kg. Flow rates can be used to differentiate grades or provide a measure of degradation of a material as a result of molding. In the present disclosure, “melt flow rate” is measured per ASTM D1238-04c Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer, as known in the art. If a melt flow rate of a particular polymer is specified, unless otherwise stated, it is the melt flow rate for that polymer alone, in the absence of any of the other components of the electrostatic ink composition.
  • acidity refers to the mass of potassium hydroxide (KOH) in milligrams that neutralizes one gram of a substance.
  • KOH potassium hydroxide
  • the acidity of a polymer can be measured according to standard techniques, for example as described in ASTM D1386. If the acidity of a particular polymer is specified, unless otherwise stated, it is the acidity for that polymer alone, in the absence of any of the other components of the liquid toner composition.
  • melt viscosity generally refers to the ratio of shear stress to shear rate at a given shear stress or shear rate. Testing is generally performed using a capillary rheometer. A plastic charge is heated in the rheometer barrel and is forced through a die with a plunger. The plunger is pushed either by a constant force or at constant rate depending on the equipment. Measurements are taken once the system has reached steady-state operation. One method used is measuring Brookfield viscosity at 140°C, units are mPa.s or cPoise, as known in the art. Alternatively, the melt viscosity can be measured using a rheometer, e.g.
  • melt viscosity of a particular polymer is specified, unless otherwise stated, it is the melt viscosity for that polymer alone, in the absence of any of the other components of the electrostatic ink composition.
  • a certain monomer may be described herein as constituting a certain weight percentage of a polymer. This indicates that the repeating units formed from the said monomer in the polymer constitute said weight percentage of the polymer.
  • electrostatic printing or “electrophotographic printing” generally refers to the process that provides an image that is transferred from a photo imaging substrate either directly or indirectly via an intermediate transfer member to a print substrate. As such, the image is not substantially absorbed into the photo imaging substrate on which it is applied.
  • electrostatic printers or “electrostatic printers” generally refer to those printers capable of performing electrophotographic printing or electrostatic printing, as described above.
  • Liquid electrophotographic printing is a specific type of electrophotographic printing where a liquid composition is employed in the electrophotographic process rather than a powder toner.
  • An electrostatic printing process may involve subjecting the electrostatic composition to an electric field, e.g.
  • the term "about” is used to provide flexibility to a numerical range endpoint by providing that a given value may be a little above or a little below the endpoint to allow for variation in test methods or apparatus. The degree of flexibility of this term can be dictated by the particular variable as would be understood in the art.
  • wt% values are to be taken as referring to a weight-for-weight (w/w) percentage of solids in the ink composition, and not including the weight of any carrier fluid present.
  • a flexible package comprising a flexible packaging material according to claim 11.
  • Document WO2016074717 A discloses a flexible packaging material and the method of preparation thereof.
  • Much research has been carried out in recent years to try to develop laminated flexible packaging materials comprising a functional (barrier) substrate laminated to a second substrate comprising a printed image or information.
  • Some existing laminated flexible packaging materials have been found to be unsuitable for use in particular circumstances, such as storage of particular items (e.g. food, detergent, chemical), package storage conditions (e.g. humid conditions which may be found in particular geographical locations, or in refrigerators or freezers), and high performance flexible packaging in which packages are required to withstand, for example, processes for extending the shelf life or food such as pasteurization and retort.
  • Printed images or information on some existing laminated flexible packaging materials have been found to discolour on heating, for example on heat sealing of a package or lamination bond strength of some existing laminated flexible packages may be found to decrease on heating causing defects between the layers during thermal processes such as pasteurization and retort.
  • the solutions proposed today consist on applying an adhesive coating on the printed substrate and laminating the coated printed substrate with a second substrate such as film, foil, paper or laminate.
  • Adhesive coatings require a prolonged period of curing (over seven days) to overcome regulatory issues and to allow adhesive coatings to reach maximum strength before moving to the next converting processes.
  • conventional laminating technologies negate the advantage of short turnaround on the printing process due to long post-printing processes/wait times.
  • examples of the process as described herein avoid or at least mitigate at least one of the difficulties described above. They have found that examples of the process are more successful than previous processes in that the lamination and bonding is immediate such that no cure time is required (zero cure time).
  • the process described can be implemented in-line with a conventional electrostatic printing process, thus further streamlining the process for producing flexible packaging materials.
  • a flexible packaging material is described.
  • the flexible packaging material may be produced by any of the methods described herein. Each component of the flexible packaging material will be discussed in the sections which follow.
  • the flexible packaging material comprises a laminate structure with sufficient bond strength to avoid delamination of the layers, in particular delamination at the interface between the second flexible substrate on which a thermally activatable laminating material is laminated and the surface of the first flexible substrate printed with the ink composition.
  • the lamination bond strength is measured directly after the flexible packaging material has cooled to room temperature following lamination, without having been subjected to any curing or rest period following lamination and cooling. In one example, the lamination bond strength is measured according to ASTM F0904-98R08.
  • the flexible packaging material has a lamination bond strength of at least about 1.0 N/inch, for example at least about 1.5 N/inch, for example at least about 2.0 N/inch, for example at least about 2.5 N/inch, for example at least about 3.0 N/inch, for example at least about 4.0 N/inch, for example at least about 5.0 N/inch, for example at least about 6.0 N/inch, for example at least about 7.0 N/inch, for example at least about 8.0 N/inch, for example at least about 9.0 N/inch, for example about 10.0 N/inch, as measured by ASTM F0904-98R08.
  • the flexible substrate, to which the primer comprising poly(acrylic acid) and/or poly(methacrylic acid) is coated and to which a liquid electrophotographic printing ink composition is to be printed may be any material suitable for use in a printing process and suitable for use in a flexible packaging material. Since the first flexible substrate forms the outermost layer of the final, laminated flexible packaging material as prepared in the methods described herein, in one example the flexible substrate is transparent in order that the printed image or information is visible to the consumer.
  • the first flexible substrate comprises a film of a polymer, for example a thermoplastic polymer.
  • the first flexible substrate comprises a film of biaxially oriented polypropylene (BOPP), polyethylene terephthalate (PET), polypropylene (PP) and oriented polyamide (OPA).
  • BOPP biaxially oriented polypropylene
  • PET polyethylene terephthalate
  • PP polypropylene
  • OPA oriented polyamide
  • suitable polymers will be known in the art and the examples provided above should be seen as non-limiting examples only.
  • the first flexible substrate comprises a thin film of a polymer, wherein the film is less than 100 ⁇ m in thickness, for example less than 90 ⁇ m in thickness, less than 80 ⁇ m in thickness, less than 70 ⁇ m in thickness, less than 60 ⁇ m in thickness, less than 50 ⁇ m in thickness, less than 40 ⁇ m in thickness, less than 30 ⁇ m in thickness, less than 20 ⁇ m in thickness, less than 15 ⁇ m in thickness.
  • the film of polymer is about 10 ⁇ m in thickness.
  • the first flexible substrate comprises a thin film of a polymer, wherein the film is greater than 10 ⁇ m in thickness, for example greater than 15 ⁇ m in thickness, greater than 20 ⁇ m in thickness, greater than 30 ⁇ m in thickness, greater than 40 ⁇ m in thickness, greater than 50 ⁇ m in thickness, greater than 60 ⁇ m in thickness, greater than 70 ⁇ m in thickness, greater than 80 ⁇ m in thickness, greater than 90 ⁇ m in thickness.
  • the film of polymer is about 100 ⁇ m in thickness.
  • the first flexible substrate has a surface on which a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) is disposed, the ink composition being then disposed on a surface of the first flexible substrate.
  • the primer comprises poly(acrylic acid).
  • the primer may comprise a copolyester.
  • the copolyester may be formed when modifications are made to polyesters, which are combinations of diacids and diols.
  • the copolyester is formed by introducing other diacids, such as isophthalic acid, or other diols, such as cyclohexane dimethanol to the polyester.
  • the material becomes a copolyester due to its comonomer content.
  • the comonomer content is of 1-50 wt% of the copolyester.
  • the primer comprising poly(acrylic acid) and/or poly(methacrylic acid) on the surface of the flexible print substrate surface is provided in an amount such that the coat weight of the primer comprising poly(acrylic acid) and/or poly(methacrylic acid) on the print substrate is at least 0.01 g/m 2 , in some examples at least 0.05 g/m 2 , in some examples at least 0.1 g/m 2 , in some examples at least 0.15 g/m 2 , in some examples about 0.18 g/m 2 .
  • the primer comprising poly(acrylic acid) and/or poly(methacrylic acid) is provided in an amount such that the coat weight of the primer comprising poly(acrylic acid) and/or poly(methacrylic acid) on the print substrate is up to about 0.2 g/m 2 , in some examples up to about 0.5 g/m 2 , in some examples up to about 1 g/m 2 , in some examples up to about 1.5 g/m 2 .
  • the first flexible substrate coated with a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) is a Sarafil® product (available from Polyplex).
  • the first flexible substrate coated with a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) is a Sarafil® DP product of Polyplex in which the first flexible substrate is a biaxyally oriented polyethylene terephthalate (BOPET) material, such as Sarafil® DP100-1G.
  • BOPET biaxyally oriented polyethylene terephthalate
  • the first flexible substrate coated with a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) is a Sarafil® DB product of Polyplex in which the first flexible substrate is a biaxyally oriented polypropylene (BOPP) material, such as Sarafil® DB100-1GO.
  • BOPP biaxyally oriented polypropylene
  • the ink composition printed on the first flexible substrate coated with the primer comprising poly(acrylic acid) and/or poly(methacrylic acid) described herein is a Liquid Electrophotographic Printing.
  • a LEP composition useful in the methods described herein to form flexible packaging materials also described generally comprises a colorant or pigment, a polymer resin and a carrier fluid or liquid.
  • the LEP composition may further comprise one or more additives such as charge directors, charge adjuvants, surfactants, viscosity modifiers, emulsifiers and the like.
  • the LEP composition may not contain any pigment, or comprise substantially zero pigment and thus be a pigment-free composition, useful in providing a particular transparent gloss or sheen to a printed substrate.
  • the LEP composition printed on the first flexible substrate described herein may comprise a reduced amount of carrier liquid compared with the LEP printing composition before printing.
  • the LEP composition printed on the first flexible substrate coated with the primer comprising poly(acrylic acid) and/or poly(methacrylic acid) described herein may be substantially free from carrier liquid. Substantially free from carrier liquid may indicate that the ink printed on the first flexible substrate contains less than 5 wt% carrier liquid, in some examples, less than 2 wt% carrier liquid, in some examples less than 1 wt% carrier liquid, in some examples less than 0.5 wt% carrier liquid. In some examples, the LEP composition printed on the first flexible substrate is free from carrier liquid.
  • the LEP composition may comprise a colorant.
  • the colorant may be a dye or pigment.
  • the colorant can be any colorant compatible with the liquid carrier and useful for electrophotographic printing.
  • the colorant may be present as pigment particles, or may comprise a resin (in addition to the polymers described herein) and a pigment.
  • the resins and pigments can be any of those commonly used as known in the art.
  • the colorant is selected from a cyan pigment, a magenta pigment, a yellow pigment and a black pigment.
  • pigments by Hoechst including Permanent Yellow DHG, Permanent Yellow GR, Permanent Yellow G, Permanent Yellow NCG-71 , Permanent Yellow GG, Hansa Yellow RA, Hansa Brilliant Yellow 5GX-02, Hansa Yellow X, NOVAPERM® YELLOW HR, NOVAPERM® YELLOW FGL, Hansa Brilliant Yellow 10GX, Permanent Yellow G3R-01 , HOSTAPERM® YELLOW H4G, HOSTAPERM® YELLOW H3G, HOSTAPERM® ORANGE GR, HOSTAPERM® SCARLET GO, Permanent Rubine F6B; pigments by Sun Chemical including L74-1357 Yellow, L75-1331 Yellow, L75- 2337 Yellow; pigments by Heubach including DALAMAR® YELLOW YT-858-D; pigments by Ciba-Geigy including CROMOPHTHAL® YELLOW 3 G, CROMOPHTHAL® YELLOW GR, CROMOPHTHAL®
  • the colorant or pigment particles may have a median particle size or d 50 of less than 20 ⁇ m, for example less than 15 ⁇ m, for example less than 10 ⁇ m, for example less than 5 ⁇ m, for example less than 4 ⁇ m, for example less than 3 ⁇ m, for example less than 2 ⁇ m, for example less than 1 ⁇ m, for example less than 0.9 ⁇ m, for example less than 08 ⁇ m, for example less than 0.7 ⁇ m, for example less than 0.6 ⁇ m, for example less than 0.5 ⁇ m.
  • the particle size of the colorant or pigment particle and the resin coated pigment particle is determined using laser diffraction on a Malvern Mastersizer 2000 according to the standard procedure as described in the operating manual.
  • the colorant or pigment particle may be present in the LEP composition in an amount of from 10 wt% to 80 wt% of the total amount of resin and pigment, in some examples 15 wt% to 80 wt%, in some examples 15 wt% to 60 wt%, in some examples 15 wt% to 50 wt%, in some examples 15 wt% to 40 wt%, in some examples 15 wt% to 30 wt% of the total amount of resin and colorant.
  • the colorant or pigment particle may be present in the LEP composition in an amount of at least 50 wt% of the total amount of resin and colorant or pigment, for example at least 55 wt% of the total amount of resin and colorant or pigment.
  • the LEP composition comprises a polymer resin which may comprise a copolymer of an alkylene monomer and a monomer selected from acrylic acid and methacrylic acid.
  • the polymer resin may be referred to as a thermopastic polymer.
  • a thermoplastic polymer is sometimes referred to as a thermoplastic resin.
  • the polymer resin may comprise one or more of ethylene or propylene acrylic acid copolymers; ethylene or propylene methacrylic acid copolymers; ethylene vinyl acetate copolymers; copolymers of ethylene or propylene (e.g. 80 wt% to 99.9 wt%), and alkyl (e.g. C 1 to C 5 ) ester of methacrylic or acrylic acid (e.g.
  • 0.1 wt% to 20 wt%) copolymers of ethylene (e.g. 80 wt% to 99.9 wt%), acrylic or methacrylic acid (e.g. 0.1 wt% to 20.0 wt%) and alkyl (e.g. C 1 to C 5 ) ester of methacrylic or acrylic acid (e.g. 0.1 wt% to 20 wt%); copolymers of ethylene or propylene (e.g. 70 wt% to 99.9 wt%) and maleic anhydride (e.g.
  • polyethylene polystyrene; isotactic polypropylene (crystalline); copolymers of ethylene ethyl acrylate; polyesters; polyvinyl toluene; polyamides; styrene/butadiene co-polymers; epoxy resins; acrylic resins (e.g. co-polymer of acrylic or methacrylic acid and at least one alkyl ester of acrylic or methacrylic acid wherein alkyl may have from 1 to about 20 carbon atoms, such as methyl methacrylate (e.g. 50% to 90%)/methacrylic acid (e.g.
  • ethylene-acrylate terpolymers ethylene-acrylic esters-maleic anhydride (MAH) or glycidyl methacrylate (GMA) terpolymers; ethylene-acrylic acid ionomers and combinations thereof.
  • MAH ethylene-acrylic esters-maleic anhydride
  • GMA glycidyl methacrylate
  • the polymer resin may comprise a polymer having acidic side groups. Examples of the polymer having acidic side groups will now be described.
  • the polymer having acidic side groups may have an acidity of 50 mg KOH/g or more, in some examples an acidity of 60 mg KOH/g or more, in some examples an acidity of 70 mg KOH/g or more, in some examples an acidity of 80 mg KOH/g or more, in some examples an acidity of 90 mg KOH/g or more, in some examples an acidity of 100 mg KOH/g or more, in some examples an acidity of 105 mg KOH/g or more, in some examples 110 mg KOH/g or more, in some examples 115 mg KOH/g or more.
  • the polymer resin having acidic side groups may have an acidity of 200 mg KOH/g or less, in some examples 190 mg or less, in some examples 180 mg or less, in some examples 130 mg KOH/g or less, in some examples 120 mg KOH/g or less.
  • Acidity of a polymer, as measured in mg KOH/g can be measured using standard procedures known in the art, for example using the procedure described in ASTM D1386.
  • the polymer resin may comprise a polymer having acidic side groups, that has a melt flow rate of less than about 70 g/10 minutes, in some examples about 60 g/10 minutes or less, in some examples about 50 g/10 minutes or less, in some examples about 40 g/10 minutes or less, in some examples 30 g/10 minutes or less, in some examples 20 g/10 minutes or less, in some examples 10 g/10 minutes or less.
  • all polymers having acidic side groups and/or ester groups in the particles each individually have a melt flow rate of less than 90 g/10 minutes, 80 g/10 minutes or less, in some examples 80 g/10 minutes or less, in some examples 70 g/10 minutes or less, in some examples 70 g/10 minutes or less, in some examples 60 g/10 minutes or less.
  • the polymer having acidic side groups can have a melt flow rate of about 10 g/10 minutes to about 120 g/10 minutes, in some examples about 10 g/10 minutes to about 70 g/10 minutes, in some examples about 10 g/10 minutes to 40 g/10 minutes, in some examples 20 g/10 minutes to 30 g/10 minutes.
  • the polymer having acidic side groups can have a melt flow rate of, in some examples, about 50 g/10 minutes to about 120 g/10 minutes, in some examples 60 g/10 minutes to about 100 g/10 minutes.
  • the melt flow rate can be measured using standard procedures known in the art, for example as described in ASTM D1238.
  • the acidic side groups may be in free acid form or may be in the form of an anion and associated with one or more counterions, typically metal counterions, e.g. a metal selected from the alkali metals, such as lithium, sodium and potassium, alkali earth metals, such as magnesium or calcium, and transition metals, such as zinc.
  • the polymer having acidic sides groups can be selected from resins such as copolymers of ethylene and an ethylenically unsaturated acid of either acrylic acid or methacrylic acid; and ionomers thereof, such as methacrylic acid and ethylene-acrylic or methacrylic acid copolymers which are at least partially neutralized with metal ions (e.g.
  • the polymer comprising acidic side groups can be a copolymer of ethylene and an ethylenically unsaturated acid of either acrylic or methacrylic acid, where the ethylenically unsaturated acid of either acrylic or methacrylic acid constitute from 5 wt% to about 25 wt% of the copolymer, in some examples from 10 wt% to about 20 wt% of the copolymer.
  • the polymer resin may comprise two different polymers having acidic side groups.
  • the two polymers having acidic side groups may have different acidities, which may fall within the ranges mentioned above.
  • the resin may comprise a first polymer having acidic side groups that has an acidity of from 10 mg KOH/g to 110 mg KOH/g, in some examples 20 mg KOH/g to 110 mg KOH/g, in some examples 30 mg KOH/g to 110 mg KOH/g, in some examples 50 mg KOH/g to 110 mg KOH/g, and a second polymer having acidic side groups that has an acidity of 110 mg KOH/g to 130 mg KOH/g.
  • the polymer resin may comprise two different polymers having acidic side groups: a first polymer having acidic side groups that has a melt flow rate of about 10 g/10 minutes to about 50 g/10 minutes and an acidity of from 10 mg KOH/g to 110 mg KOH/g, in some examples 20 mg KOH/g to 110 mg KOH/g, in some examples 30 mg KOH/g to 110 mg KOH/g, in some examples 50 mg KOH/g to 110 mg KOH/g, and a second polymer having acidic side groups that has a melt flow rate of about 50 g/10 minutes to about 120 g/10 minutes and an acidity of 110 mg KOH/g to 130 mg KOH/g.
  • the first and second polymers may be absent of ester groups.
  • the ratio of the first polymer having acidic side groups to the second polymer having acidic side groups can be from about 10:1 to about 2:1.
  • the ratio can be from about 6:1 to about 3:1, in some examples about 4:1.
  • the polymer resin may comprise a polymer having a melt viscosity of 15000 poise or less, in some examples a melt viscosity of 10000 poise or less, in some examples 1000 poise or less, in some examples 100 poise or less, in some examples 50 poise or less, in some examples 10 poise or less; said polymer may be a polymer having acidic side groups as described herein.
  • the polymer resin may comprise a first polymer having a melt viscosity of 15000 poise or more, in some examples 20000 poise or more, in some examples 50000 poise or more, in some examples 70000 poise or more; and in some examples, the resin may comprise a second polymer having a melt viscosity less than the first polymer, in some examples a melt viscosity of 15000 poise or less, in some examples a melt viscosity of 10000 poise or less, in some examples 1000 poise or less, in some examples 100 poise or less, in some examples 50 poise or less, in some examples 10 poise or less.
  • the polymer resin may comprise a first polymer having a melt viscosity of more than 60000 poise, in some examples from 60000 poise to 100000 poise, in some examples from 65000 poise to 85000 poise; a second polymer having a melt viscosity of from 15000 poise to 40000 poise, in some examples 20000 poise to 30000 poise, and a third polymer having a melt viscosity of 15000 poise or less, in some examples a melt viscosity of 10000 poise or less, in some examples 1000 poise or less, in some examples 100 poise or less, in some examples 50 poise or less, in some examples 10 poise or less; an example of the first polymer is Nucrel® 960 (from DuPont), and example of the second polymer is Nucrel® 699 (from DuPont), and an example of the third polymer is A-C® 5120 or A-C® 5180 (from Honeywell).
  • the first, second and third polymers may be polymers having acidic side groups as described herein.
  • the melt viscosity can be measured using a rheometer, e.g. a commercially available AR-2000 Rheometer from Thermal Analysis Instruments, using the geometry of: 25mm steel plate-standard steel parallel plate, and finding the plate over plate rheometry isotherm at 120°C, 0.01 Hz shear rate.
  • the polymer may have a melt viscosity of 6000 poise or more, in some examples a melt viscosity of 8000 poise or more, in some examples a melt viscosity of 10000 poise or more, in some examples a melt viscosity of 12000 poise or more.
  • the resin comprises a plurality of polymers
  • all the polymers of the polymer resin may together form a mixture (excluding any other components of the electrophotographic ink composition) that has a melt viscosity of 6000 poise or more, in some examples a melt viscosity of 8000 poise or more, in some examples a melt viscosity of 10000 poise or more, in some examples a melt viscosity of 12000 poise or more.
  • Melt viscosity can be measured using standard techniques. The melt viscosity can be measured using a rheometer, e.g. a commercially available AR-2000 Rheometer from Thermal Analysis Instruments, using the geometry of: 25mm steel plate-standard steel parallel plate, and finding the plate over plate rheometry isotherm at 120°C, 0.01 Hz shear rate.
  • the polymer resin may comprise two different polymers having acidic side groups that are selected from copolymers of ethylene and an ethylenically unsaturated acid of either acrylic acid or methacrylic acid; or ionomers thereof, such as methacrylic acid and ethylene-acrylic or methacrylic acid copolymers which are at least partially neutralized with metal ions (e.g. Zn, Na, Li) such as Surlyn® ionomers.
  • metal ions e.g. Zn, Na, Li
  • the polymer resin may comprise (i) a first polymer that is a copolymer of ethylene and an ethylenically unsaturated acid of either acrylic acid and methacrylic acid, wherein the ethylenically unsaturated acid of either acrylic or methacrylic acid constitutes from 8 wt% to about 16 wt% of the copolymer, in some examples 10 wt% to 16 wt% of the copolymer; and (ii) a second polymer that is a copolymer of ethylene and an ethylenically unsaturated acid of either acrylic acid and methacrylic acid, wherein the ethylenically unsaturated acid of either acrylic or methacrylic acid constitutes from 12 wt% to about 30 wt% of the copolymer, in some examples from 14 wt% to about 20 wt% of the copolymer, in some examples from 16 wt% to about 20 wt% of the copolymer in some examples from
  • the polymer resin may comprise a polymer having acidic side groups, as described above (which may be free of ester side groups), and a polymer having ester side groups.
  • the polymer having ester side groups may be a thermoplastic polymer.
  • the polymer having ester side groups may further comprise acidic side groups.
  • the polymer having ester side groups may be a copolymer of a monomer having ester side groups and a monomer having acidic side groups.
  • the polymer may be a copolymer of a monomer having ester side groups, a monomer having acidic side groups, and a monomer absent of any acidic and ester side groups.
  • the monomer having ester side groups may be a monomer selected from esterified acrylic acid or esterified methacrylic acid.
  • the monomer having acidic side groups may be a monomer selected from acrylic or methacrylic acid.
  • the monomer absent of any acidic and ester side groups may be an alkylene monomer, including, for example, ethylene or propylene.
  • the esterified acrylic acid or esterified methacrylic acid may, respectively, be an alkyl ester of acrylic acid or an alkyl ester of methacrylic acid.
  • the alkyl group in the alkyl ester of acrylic or methacrylic acid may be an alkyl group having 1 to 30 carbons, in some examples 1 to 20 carbons, in some examples 1 to 10 carbons; in some examples selected from methyl, ethyl, iso-propyl, n-propyl, t-butyl, iso-butyl, n-butyl and pentyl.
  • the polymer having ester side groups may be a copolymer of a first monomer having ester side groups, a second monomer having acidic side groups and a third monomer which is an alkylene monomer absent of any acidic and ester side groups.
  • the polymer having ester side groups may be a copolymer of (i) a first monomer having ester side groups selected from esterified acrylic acid or esterified methacrylic acid, in some examples an alkyl ester of acrylic or methacrylic acid, (ii) a second monomer having acidic side groups selected from acrylic or methacrylic acid and (iii) a third monomer which is an alkylene monomer selected from ethylene and propylene.
  • the first monomer may constitute 1% to 50% by weight of the copolymer, in some examples 5% to 40% by weight, in some examples 5% to 20% by weight of the copolymer, in some examples 5% to 15% by weight of the copolymer.
  • the second monomer may constitute 1% to 50 % by weight of the copolymer, in some examples 5% to 40% by weight of the copolymer, in some examples 5% to 20% by weight of the co-polymer, in some examples 5% to 15% by weight of the copolymer.
  • the first monomer can constitute 5% to 40% by weight of the copolymer, the second monomer constitutes 5% to 40% by weight of the copolymer, and with the third monomer constituting the remaining weight of the copolymer.
  • the first monomer constitutes 5% to 15% by weight of the copolymer
  • the second monomer constitutes 5% to 15% by weight of the copolymer, with the third monomer constituting the remaining weight of the copolymer.
  • the first monomer constitutes 8% to 12% by weight of the copolymer
  • the second monomer constitutes 8% to 12% by weight of the copolymer, with the third monomer constituting the remaining weight of the copolymer.
  • the first monomer constitutes about 10% by weight of the copolymer
  • the second monomer constitutes about 10% by weight of the copolymer
  • the polymer may be selected from the Bynel® class of monomer, including Bynel 2022 and Bynel 2002, which are available from DuPont.
  • the polymer having ester side groups may constitute 1% or more by weight of the total amount of the resin polymers, e.g. thermoplastic resin polymers, in the liquid electrophotographic ink composition printed on the print substrate, e.g. the total amount of the polymer or polymers having acidic side groups and polymer having ester side groups.
  • the polymer having ester side groups may constitute 5% or more by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in some examples 8% or more by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in some examples 10% or more by weight of the total amount of the resin polymers, e.g.
  • thermoplastic polymers in some examples 15% or more by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in some examples 20% or more by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in some examples 25% or more by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in some examples 30% or more by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in some examples 35% or more by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in the LEP composition printed on the print substrate.
  • the polymer having ester side groups may constitute from 5% to 50% by weight of the total amount of the resin polymers, e.g.
  • thermoplastic resin polymers, in the LEP composition printed on the print substrate in some examples 10% to 40% by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in the LEP composition printed on the print substrate, in some examples 5% to 30% by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in the LEP composition printed on the print substrate, in some examples 5% to 15% by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in the LEP composition printed on the print substrate, in some examples 15% to 30% by weight of the total amount of the resin polymers, e.g. thermoplastic polymers, in the LEP composition printed on the print substrate.
  • the polymer having ester side groups may have an acidity of 50 mg KOH/g or more, in some examples an acidity of 60 mg KOH/g or more, in some examples an acidity of 70 mg KOH/g or more, in some examples an acidity of 80 mg KOH/g or more.
  • the polymer having ester side groups may have an acidity of 100 mg KOH/g or less, in some examples 90 mg KOH/g or less.
  • the polymer having ester side groups may have an acidity of 60 mg KOH/g to 90 mg KOH/g, in some examples 70 mg KOH/g to 80 mg KOH/g.
  • the polymer having ester side groups may have a melt flow rate of about 10 g/10 minutes to about 120 g/10 minutes, in some examples about 10 g/10 minutes to about 50 g/10 minutes, in some examples about 20 g/10 minutes to about 40 g/10 minutes, in some examples about 25 g/10 minutes to about 35 g/10 minutes.
  • the polymer, polymers, copolymer or copolymers of the thermoplastic resin can in some examples be selected from the Nucrel® family of toners (e.g. Nucrel® 403, Nucrel® 407, Nucrel® 609HS, Nucrel® 908HS, Nucrel® 1202HC, Nucrel® 30707, Nucrel® 1214, Nucrel® 903, Nucrel® 3990, Nucrel® 910, Nucrel® 925, Nucrel® 699, Nucrel® 599, Nucrel® 960, Nucrel® RX 76, Nucrel® 2806, Bynel® 2002, Bynel® 2014, Bynel® 2020 and Bynel® 2022, (sold by DuPont)), the A-C® family of toners (e.g.
  • AClyn® family of toners e.g. AClyn® 201, AClyn® 246, AClyn® 285 and AClyn® 295
  • the Lotader® family of toners e.g. Lotader® 2210, Lotader® 3430 and Lotader® 8200 (sold by Arkema)
  • the polymer resin can constitute about 5 to 90%, in some examples about 50 to 80%, by weight of the solids of the LEP composition printed onto the surface of the first flexible substrate.
  • the resin can constitute about 60 to 95%, in some examples about 70 to 95%, by weight of the solids of the LEP composition printed onto the surface of the first flexible substrate.
  • the LEP composition comprises polymer resin coated pigment particles, or resin particles, which are formed in and/or dispersed in a carrier fluid or carrier liquid.
  • the ink composition Before application to the print substrate in the electrostatic printing process, the ink composition may be an electrostatic ink composition, which may be in dry form, for example in the form of flowable pigment particles coated with the thermoplastic resin.
  • the electrostatic ink composition before application to the print substrate in the electrostatic printing process, may be in liquid form; and may comprise a carrier liquid in which is suspended pigment particles coated with the thermoplastic resin.
  • the carrier liquid acts as a reaction solvent in preparing the coated pigment particles, and can also act as a dispersing medium for the other components in the resulting electrostatic ink composition.
  • the carrier liquid is a liquid which does not dissolve the polymer resin at room temperature.
  • the carrier liquid is a liquid which dissolves the polymer resin at elevated temperatures.
  • the polymer resin may be soluble in the carrier liquid when heated to a temperature of at least 80°C, for example 90°C, for example 100°C, for example 110°C, for example 120°C.
  • the carrier liquid can comprise or be a hydrocarbon, silicone oil, vegetable oil, etc.
  • the carrier liquid can include, but is not limited to, an insulating, non-polar, non-aqueous liquid that can be used as a medium for toner particles.
  • the carrier liquid can include compounds that have a resistivity in excess of about 10 9 ohm-cm.
  • the carrier liquid may have a dielectric constant below about 5, in some examples below about 3.
  • the carrier liquid can include hydrocarbons.
  • the hydrocarbon can include an aliphatic hydrocarbon, an isomerized aliphatic hydrocarbon, branched chain aliphatic hydrocarbons, aromatic hydrocarbons, and combinations thereof. Examples of the carrier liquids include aliphatic hydrocarbons, isoparaffinic compounds, paraffinic compounds, dearomatized hydrocarbon compounds, and the like.
  • the carrier liquids can include Isopar-GTM, Isopar-HTM, Isopar-LTM, Isopar-MTM, Isopar-KTM, Isopar-VTM, Norpar 12TM, Norpar 13TM, Norpar 15TM, Exxol D40TM, Exxol D80TM, Exxol D100TM, Exxol D130TM, and Exxol D140TM (each sold by EXXON CORPORATION); Teclen N-16TM, Teclen N-20TM, Teclen N-22TM, Nisseki Naphthesol LTM, Nisseki Naphthesol MTM, Nisseki Naphthesol HTM, #0 Solvent LTM, #0 Solvent MTM, #0 Solvent HTM, Nisseki Isosol 300TM, Nisseki Isosol 400TM, AF-4TM, AF-5TM, AF-6TM and AF-7TM (each sold by NIPPON OIL CORPORATION
  • the carrier liquid Before printing, the carrier liquid can constitute about 20% to 99.5% by weight of the electrostatic ink composition, in some examples 50% to 99.5% by weight of the electrostatic ink composition. Before printing, the carrier liquid may constitute about 40 to 90% by weight of the electrostatic ink composition. Before printing, the carrier liquid may constitute about 60% to 80% by weight of the electrostatic ink composition. Before printing, the carrier liquid may constitute about 90% to 99.5% by weight of the electrostatic ink composition, in some examples 95% to 99% by weight of the electrostatic ink composition.
  • the electrostatic ink composition when printed onto the surface of the first flexible substrate, may be substantially free from carrier liquid.
  • the carrier liquid may be removed, e.g. by an electrophoresis processes during printing and/or evaporation, such that substantially just solids are transferred to the print substrate.
  • Substantially free from carrier liquid may indicate that the ink printed onto the surface of the first flexible substrate contains less than 5 wt% carrier liquid, in some examples, less than 2 wt% carrier liquid, in some examples less than 1 wt% carrier liquid, in some examples less than 0.5 wt% carrier liquid.
  • the ink printed onto the surface of the first flexible substrate is free from carrier liquid.
  • the ink composition printed onto the surface of the first flexible substrate can comprise a charge director.
  • a charge director can be added to an electrostatic composition to impart a charge of a desired polarity and/or maintain sufficient electrostatic charge on the particles of an electrostatic ink composition.
  • the charge director may comprise ionic compounds, including, for example, metal salts of fatty acids, metal salts of sulfo-succinates, metal salts of oxyphosphates, metal salts of alkyl-benzenesulfonic acid, metal salts of aromatic carboxylic acids or sulfonic acids, as well as zwitterionic and non-ionic compounds, such as polyoxyethylated alkylamines, lecithin, polyvinylpyrrolidone, organic acid esters of polyvalent alcohols, etc.
  • the charge director can be selected from oil-soluble petroleum sulfonates (e.g. neutral Calcium PetronateTM, neutral Barium PetronateTM, and basic Barium PetronateTM), polybutylene succinimides (e.g. OLOATM 1200 and Amoco 575), and glyceride salts (e.g. sodium salts of phosphated mono- and diglycerides with unsaturated and saturated acid substituents), sulfonic acid salts including, for example, barium, sodium, calcium, and aluminium salts of sulfonic acid.
  • oil-soluble petroleum sulfonates e.g. neutral Calcium PetronateTM, neutral Barium PetronateTM, and basic Barium PetronateTM
  • polybutylene succinimides e.g. OLOATM 1200 and Amoco 575
  • glyceride salts e.g. sodium salts of phosphated mono- and diglycerides with unsaturated and saturated acid substituents
  • the sulfonic acids may include, for example, alkyl sulfonic acids, aryl sulfonic acids, and sulfonic acids of alkyl succinates (e.g. see WO 2007/130069 ).
  • the charge director can impart a negative charge or a positive charge on the resin-containing particles of an electrostatic ink composition.
  • the charge director can comprise a sulfosuccinate moiety of the general formula: [R a -O-C(O)CH 2 CH(SO 3 - )C(O)-O-R b ], where each of R a and R b is an alkyl group.
  • the charge director comprises nanoparticles of a simple salt and a sulfosuccinate salt of the general formula MA n , wherein M is a metal, n is the valence of M, and A is an ion of the general formula [R a -O-C(O)CH 2 CH(SO 3 - )C(O)-O-R b ], where each of R a and R b is an alkyl group, or other charge directors as found in WO 2007/130069 , which is incorporation herein by reference in its entirety.
  • the sulfosuccinate salt of the general formula MA n is an example of a micelle forming salt.
  • the charge director may be substantially free or free of an acid of the general formula HA, where A is as described above.
  • the charge director may comprise micelles of said sulfosuccinate salt enclosing at least some of the nanoparticles.
  • the charge director may comprise at least some nanoparticles having a size of 200 nm or less, in some examples 2 nm or more.
  • simple salts are salts that do not form micelles by themselves, although they may form a core for micelles with a micelle forming salt.
  • the ions constructing the simple salts are all hydrophilic.
  • the simple salt may comprise a cation selected from Mg, Ca, Ba, NH 4 , tert-butyl ammonium, Li + , and Al 3+ , or from any subgroup thereof.
  • the simple salt may comprise an anion selected from SO 4 2- , PO 3- , NO 3- , HPO 4 2- , CO 3 2- , acetate, trifluoroacetate (TFA), Cl - , Bf, F - , ClO 4 - , and TiO 3 4- , or from any sub-group thereof.
  • the simple salt may be selected from CaCO 3 , Ba 2 TiO 3 , Al 2 (SO 4 ), Al(NO 3 ) 3 , Ca 3 (PO 4 ) 2 , BaSO 4 , BaHPO 4 , Ba 2 (PO 4 ) 3 , CaSO 4 , (NH 4 ) 2 CO 3 , (NH 4 ) 2 SO 4 , NH 4 OAc, tert-butyl ammonium bromide, NH 4 NO 3 , LiTFA, Al 2 (SO 4 ) 3 , LiClO 4 and LiBF 4 , or any sub-group thereof.
  • the charge director may further comprise basic barium petronate (BBP).
  • each of R a and R b is an aliphatic alkyl group.
  • each of R a and R b independently is a C 6-25 alkyl.
  • said aliphatic alkyl group is linear.
  • said aliphatic alkyl group is branched.
  • said aliphatic alkyl group includes a linear chain of more than 6 carbon atoms.
  • R a and R b are the same.
  • at least one of R a and R b is C 13 H 27 .
  • M is Na, K, Cs, Ca, or Ba.
  • the formula [R a -O-C(O)CH 2 CH(SO 3 - )C(O)-O-R b ] and/or the formula MA n may be as defined in any part of WO 2007/130069 .
  • the charge director may comprise (i) soya lecithin, (ii) a barium sulfonate salt, such as basic barium petronate (BPP), and (iii) an isopropyl amine sulfonate salt.
  • BPP basic barium petronate
  • An example isopropyl amine sulphonate salt is dodecyl benzene sulfonic acid isopropyl amine, which is available from Croda.
  • the charge director can constitute about 0.001% to 20%, in some examples 0.01 to 20% by weight, in some examples 0.01 to 10% by weight, in some examples 0.01 to 1% by weight of the solids of the electrostatic ink composition printed onto the surface of the first flexible substrate.
  • the charge director can constitute about 0.001 to 0.15% by weight of the solids of the liquid electrophotographic ink composition printed onto the surface of the first flexible substrate, in some examples 0.001 to 0.15%, in some examples 0.001 to 0.02% by weight of the solids of the liquid electrophotographic ink composition printed onto the surface of the first flexible substrate.
  • the charge director imparts a negative charge on the electrostatic ink composition.
  • the particle conductivity may range from 50 to 500 pmho/cm, in some examples from 200-350 pmho/cm.
  • the ink composition printed onto the surface of the first flexible substrate can comprise a charge adjuvant.
  • a charge adjuvant may be present with a charge director, and may be different to the charge director, and act to increase and/or stabilise the charge on particles, e.g. resin-containing particles, of an electrostatic composition.
  • the charge adjuvant can include, for example, barium petronate, calcium petronate, Co salts of naphthenic acid, Ca salts of naphthenic acid, Cu salts of naphthenic acid, Mn salts of naphthenic acid, Ni salts of naphthenic acid, Zn salts of naphthenic acid, Fe salts of naphthenic acid, Ba salts of stearic acid, Co salts of stearic acid, Pb salts of stearic acid, Zn salts of stearic acid, Al salts of stearic acid, Cu salts of stearic acid, Fe salts of stearic acid, metal carboxylates (e.g.
  • the charge adjuvant is aluminium di and/or tristearate and/or aluminium di and/or tripalmitate.
  • the charge adjuvant can constitute about 0.1 to 5% by weight of the solids of the liquid electrophotographic ink composition printed onto the surface of the first flexible substrate.
  • the charge adjuvant can constitute about 0.5 to 4% by weight of the solids of the liquid electrophotographic ink composition printed onto the surface of the first flexible substrate.
  • the charge adjuvant can constitute about 1 to 3% by weight of the solids of the liquid electrophotographic ink composition printed onto the surface of the first flexible substrate.
  • the electrophotographic ink composition may include an additive or a plurality of additives.
  • the additive or plurality of additives may be added at any stage of the method.
  • the additive or plurality of additives may be selected from a wax, a surfactant, biocides, organic solvents, viscosity modifiers, materials for pH adjustment, sequestering agents, preservatives, compatibility additives, emulsifiers and the like.
  • the wax may be an incompatible wax.
  • incompatible wax may refer to a wax that is incompatible with the resin. Specifically, the wax phase separates from the resin phase upon the cooling of the resin fused mixture on a print substrate during and after the transfer of the ink film to the print substrate, e.g. from an intermediate transfer member, which may be a heated blanket.
  • the second flexible substrate may also be referred to as a functional substrate or simply a base layer.
  • the base layer of the flexible packaging material may be the innermost layer of the flexible packaging material in use, and may thus be in contact with the packaged goods.
  • the base layer is referred to as a functional substrate and is functional in the sense that it provides a barrier function to protect the packaged goods.
  • the base layer or functional substrate may serve as a barrier to any external influence that could damage or otherwise reduce the quality of the packaged goods, in particular food, by preventing ingress of, for example, moisture, oxygen, other oxidants and pathogens such as viruses and bacteria.
  • the second flexible substrate comprises a thin film or thin sheet of paper, metallic foil, and/or a plastic material.
  • the second flexible substrate comprises a metallic foil or a metallized substrate.
  • the second flexible substrate comprises an aluminium foil.
  • the second flexible substrate comprises a thin film of a plastic material, for example, polyethylene (PE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), polypropylene (PP), cast (cPP) or axially oriented polypropylene (BOPP), oriented polyamide (OPA).
  • the second flexible substrate comprises a plurality of layers of film of a plastic material, such as a combination of films selected from PE, LLDPE, PP, BOPP, OPA, Al, metalized BOPP, metalized PET, laminated together.
  • the second flexible substrate comprises a metallized paper in the form of a paper substrate coated on one surface with a layer of metal, for example aluminium.
  • the second flexible substrate comprises a metallized plastic film in the form of a polymer substrate coated on one surface with a layer of metal, for example aluminium.
  • the second flexible substrate comprises a metallized plastic film in the form of a metallized BOPP film, a metallized PET film, or a metallized polyethylene (PE) film.
  • the metallized PET or PE is coated with a SiOx or AlOx layer.
  • the second flexible substrate comprises a thin film of material, wherein the film is less than 250 ⁇ m in thickness, for example less than 90 ⁇ m in thickness, less than 80 ⁇ m in thickness, less than 70 ⁇ m in thickness, less than 60 ⁇ m in thickness, less than 50 ⁇ m in thickness, less than 40 ⁇ m in thickness, less than 30 ⁇ m in thickness, less than 20 ⁇ m in thickness, less than 15 ⁇ m in thickness.
  • the film of material is about 12 ⁇ m in thickness.
  • the second flexible substrate comprises a thin film of material, wherein the film is greater than 12 ⁇ m in thickness, for example greater than 15 ⁇ m in thickness, greater than 20 ⁇ m in thickness, greater than 30 ⁇ m in thickness, greater than 40 ⁇ m in thickness, greater than 50 ⁇ m in thickness, greater than 60 ⁇ m in thickness, greater than 70 ⁇ m in thickness, greater than 80 ⁇ m in thickness, greater than 90 ⁇ m in thickness.
  • the film of material is about 250 ⁇ m in thickness.
  • the second flexible substrate comprises a sealant layer disposed on a surface thereof other than the surface on which the thermally activatable laminating material is applied, and thus on which the first flexible substrate printed with the ink composition is laminated.
  • the sealant layer is disposed on the innermost surface of the flexible packaging material and serves to provide means for sealing the flexible packaging material to itself or another material, with the goods to be packaged inside.
  • the sealant layer comprises a film of low-melting, i.e. heat sealable, thermoplastic material. Suitable thermoplastic materials include those described herein in connection with the polymer resin and/or the thermally activatable laminating material and include polymers of ethylene, or DuPont's Surlyn® ionomers.
  • the sealant layer comprises an extrudable material.
  • the sealant layer comprises a thin film of a polymer, wherein the film is less than 100 ⁇ m in thickness, for example less than 90 ⁇ m in thickness, less than 80 ⁇ m in thickness, less than 70 ⁇ m in thickness, less than 60 ⁇ m in thickness, less than 50 ⁇ m in thickness, less than 40 ⁇ m in thickness, less than 30 ⁇ m in thickness, less than 20 ⁇ m in thickness, less than 15 ⁇ m in thickness.
  • the film of polymer is about 5 ⁇ m in thickness.
  • the sealant layer comprises a thin film of a polymer, wherein the film is greater than 5 ⁇ m in thickness, for example greater than 15 ⁇ m in thickness, greater than 20 ⁇ m in thickness, greater than 30 ⁇ m in thickness, greater than 40 ⁇ m in thickness, greater than 50 ⁇ m in thickness, greater than 60 ⁇ m in thickness, greater than 70 ⁇ m in thickness, greater than 80 ⁇ m in thickness, greater than 90 ⁇ m in thickness.
  • the film of polymer is about 100 ⁇ m in thickness.
  • the thermally activatable laminating material may also be referred to as a thermal laminating material or layer or polymer or thermally activatable laminating layer or polymer.
  • the thermally activatable laminating material comprises a polymer resin, for example a thermoplastic polymer resin.
  • the thermally activatable laminating material comprises a low-melting polymer.
  • low-melting polymer is to be understood as a polymeric material which is solid at room temperature but melts at a temperature typically obtainable in a printing or laminating apparatus.
  • the thermally activatable laminating material may comprise a low-melting polymer with a melting point of less than about 200°C, for example less than about 190°C, for example less than about 180°C, for example less than about 170°C, for example less than about 160°C, for example less than about 150°C, for example less than about 140°C, for example less than about 130°C, for example less than about 120°C, for example less than about 110°C, for example less than about 100°C, for example less than about 90°C, for example less than about 80°C, for example about 70°C.
  • a melting point of less than about 200°C for example less than about 190°C, for example less than about 180°C, for example less than about 170°C, for example less than about 160°C, for example less than about 150°C, for example less than about 140°C, for example less than about 130°C, for example less than about 120°C, for example less than about 110°C, for example less than about 100°C
  • the thermally activatable laminating material may comprise a low-melting polymer with a melting point of greater than about 70°C, for example greater than about 80°C, for example greater than about 90°C, for example greater than about 100°C, for example greater than about 110°C, for example greater than about 120°C, for example greater than about 130°C, for example greater than about 140°C, for example greater than about 150°C, for example greater than about 160°C, for example greater than about 170°C, for example greater than about 180°C, for example greater than about 190°C, for example about 200°C.
  • a melting point of greater than about 70°C for example greater than about 80°C, for example greater than about 90°C, for example greater than about 100°C, for example greater than about 110°C, for example greater than about 120°C, for example greater than about 130°C, for example greater than about 140°C, for example greater than about 150°C, for example greater than about 160°C, for example greater than about 170°C,
  • thermally activatable laminating material By using a low-melting polymer as the thermally activatable laminating material to form the thermally activatable laminating material, it becomes possible to extrude the thermally activatable laminating material onto the second flexible substrate to form a layered structure for laminating to the printed substrate.
  • the thermally activatable laminating material comprises a thin film of a polymer, wherein the film is less than 180 ⁇ m in thickness, for example less than 160 ⁇ m in thickness, for example less than 140 ⁇ m in thickness, for example less than 120 ⁇ m in thickness, for example less than 100 ⁇ m in thickness, for example less than 80 ⁇ m in thickness, for example less than 60 ⁇ m in thickness, for example less than 50 ⁇ m in thickness, for example less than 40 ⁇ m in thickness, for example less than 30 ⁇ m in thickness, for example less than 20 ⁇ m in thickness, for example less than 10 ⁇ m in thickness, for example less than 9 ⁇ m in thickness, for example less than 8 ⁇ m in thickness, for example less than 7 ⁇ m in thickness, for example less than 6 ⁇ m in thickness, for example less than 5 ⁇ m in thickness, for example less than 4 ⁇ m in thickness, for example less than 3 ⁇ m in thickness.
  • the film of polymer is about 2 ⁇ m in thickness.
  • the thermally activatable laminating material comprises a thin film of a polymer, wherein the film is greater than 2 ⁇ m in thickness, for example greater than 3 ⁇ m in thickness, for example greater than 4 ⁇ m in thickness, for example greater than 5 ⁇ m in thickness, for example greater than 6 ⁇ m in thickness, for example greater than 7 ⁇ m in thickness, for example greater than 8 ⁇ m in thickness, for example greater than 9 ⁇ m in thickness, for example greater than 10 ⁇ m in thickness, for example greater than 20 ⁇ m in thickness, for example greater than 30 ⁇ m in thickness, for example greater than 40 ⁇ m in thickness, for example greater than 50 ⁇ m in thickness, for example greater than 60 ⁇ m in thickness, for example greater than 80 ⁇ m in thickness, for example greater than 100 ⁇ m in thickness, for example greater than 120 ⁇ m in thickness, for example greater than 140 ⁇ m in thickness, for example greater than 160 ⁇ m in thickness.
  • the film of polymer is about 180 ⁇ m in thickness.
  • the thermally activatable laminating material comprises a thin film of a polymer, wherein the film has a coating weight of less than 160 grams per square metre (gsm), for example less than 150 gsm, for example less than 140 gsm, for example less than 130 gsm, for example less than 120 gsm, for example less than 110 gsm, for example less than 100 gsm, for example less than 90 gsm, for example less than 80 gsm, for example less than 70 gsm, for example less than 60 gsm, for example less than 50 gsm, for example less than 40 gsm, for example less than 30 gsm, for example less than 20 gsm, for example less than 15 gsm, for example less than 10 gsm, for example less than 9 gsm, for example less than 8 gsm, for example less than 7 gsm, for example less than 6 gsm, for example less than 5 gsm,
  • the thermally activatable laminating material comprises a thin film of a polymer, wherein the film is greater than 2 gsm in weight, for example greater than 3 gsm, for example greater than 4 gsm, for example greater than 5 gsm, for example greater than 6 gsm, for example greater than 7 gsm, for example greater than 8 gsm, for example greater than 9 gsm, for example greater than 10 gsm, for example greater than 15 gsm, for example greater than 20 gsm, for example greater than 30 gsm, for example greater than 40 gsm, for example greater than 50 gsm, for example greater than 60 gsm, for example greater than 70 gsm, for example greater than 80 gsm, for example greater than 90 gsm, for example greater than 100 gsm, for example greater than 110 gsm, for example greater than 120 gsm, for example greater than 130 gsm, for example greater than 140
  • the thermally activatable laminating material may be a polymer selected from ethylene or propylene acrylic or methacrylic acid copolymers; ethylene or propylene methacrylic acid copolymers; ethylene vinyl acetate copolymers; copolymers of ethylene or propylene (e.g. 80 wt% to 99.9 wt%), and alkyl (e.g. C 1 to C 5 ) ester of methacrylic or acrylic acid (e.g. 0.1 wt% to 20.0 wt%; co-polymers of ethylene or propylene (e.g. 80 wt% to 99.9 wt%), acrylic or methacrylic acid (e.g.
  • 0.1 wt% to 20.0 wt%) and C 1 -C 5 alkyl ester of methacrylic or acrylic acid e.g. 0.1 wt% to 20.0 wt%); co-polymers of ethylene or propylene (e.g. 70 wt% to 99.9 wt%) and maleic anhydride (e.g.
  • polyethylene polystyrene; isotactic polypropylene (crystalline); copolymers of ethylene ethyl acrylate; polyesters; polyvinyl toluene; polyamides; styrene/butadiene copolymers; epoxu resins; acrylic resins (e.g. copolymer of acrylic or methacrylic acid and at least one C 1 -C 20 alkyl ester of acrylic or methacrylic acid, such as methyl methacrylate (e.g. 50% to 90%)/methacrylic acid (e.g.
  • ethylene-acrylate terpolymers ethylene-acrylic esters-maleic anhydride (MAH) or glycidyl methacrylate (GMA) terpolymers; ethylene-acrylic acid ionomers, urethane polymers and combinations thereof.
  • MAH ethylene-acrylic esters-maleic anhydride
  • GMA glycidyl methacrylate
  • the thermally activatable laminating material may comprise a polymer having acidic side groups.
  • the polymer having acidic side groups may have an acidity of 50 mg KOH/g or more, in some examples an acidity of 60 mg KOH/g or more, in some examples an acidity of 70 mg KOH/g or more, in some examples an acidity of 80 mg KOH/g or more, in some examples an acidity of 90 mg KOH/g or more, in some examples an acidity of 100 mg KOH/g or more, in some examples an acidity of 105 mg KOH/g or more, in some examples 110 mg KOH/g or more, in some examples 115 mg KOH/g or more.
  • the polymer having acidic side groups may have an acidity of 200 mg KOH/g or less, in some examples 190 mg or less, in some examples 180 mg or less, in some examples 170 mg or less, in some examples 160 mg or less, in some examples 150 mg or less, in some examples 140 mg or less, in some examples 130 mg KOH/g or less, in some examples 120 mg KOH/g or less.
  • Acidity of a polymer, as measured in mg KOH/g can be measured using standard procedures known in the art, for example using the procedure described in ASTM D1386.
  • the thermally activatable laminating material may comprise a polymer, in some examples a polymer having acidic side groups, that has a melt flow rate of less than about 70 g/10 minutes, in some examples about 60 g/10 minutes or less, in some examples about 50 g/10 minutes or less, in some examples about 40 g/10 minutes or less, in some examples 30 g/10 minutes or less, in some examples 20 g/10 minutes or less, in some examples 10 g/10 minutes or less.
  • all polymers having acidic side groups and/or ester groups in the particles each individually have a melt flow rate of less than 90 g/10 minutes, 80 g/10 minutes or less, in some examples 70 g/10 minutes or less, in some examples 70 g/10 minutes or less, in some examples 60 g/10 minutes or less.
  • the polymer having acidic side groups can have a melt flow rate of about 10 g/10 minutes to about 120 g/10 minutes, in some examples about 10 g/10 minutes to about 70 g/10 minutes, in some examples about 10 g/10 minutes to 40 g/10 minutes, in some examples 20 g/10 minutes to 30 g/10 minutes.
  • the polymer having acidic side groups can have a melt flow rate of, in some examples, about 50 g/10 minutes to about 120 g/10 minutes, in some examples 60 g/10 minutes to about 100 g/10 minutes.
  • the melt flow rate can be measured using standard procedures known in the art, for example as described in ASTM D1238.
  • the acidic side groups may be in free acid form or may be in the form of an anion and associated with one or more counterions, typically metal counterions, e.g. a metal selected from the alkali metals, such as lithium, sodium and potassium, alkali earth metals, such as magnesium or calcium, and transition metals, such as zinc.
  • the polymer having acidic sides groups can be selected from resins such as copolymers of ethylene and an ethylenically unsaturated acid of either acrylic acid or methacrylic acid; and ionomers thereof, such as methacrylic acid and ethylene-acrylic or methacrylic acid copolymers which are at least partially neutralized with metal ions (e.g.
  • the polymer comprising acidic side groups can be a copolymer of ethylene and an ethylenically unsaturated acid of either acrylic or methacrylic acid, where the ethylenically unsaturated acid of either acrylic or methacrylic acid constitute from 5 wt% to about 25 wt% of the co-polymer, in some examples from 10 wt% to about 20 wt% of the co-polymer.
  • the thermally activatable laminating material may comprise two different polymers having acidic side groups.
  • the two polymers having acidic side groups may have different acidities, which may fall within the ranges mentioned above.
  • the resin may comprise a first polymer having acidic side groups that has an acidity of from 10 mg KOH/g to 110 mg KOH/g, in some examples 20 mg KOH/g to 110 mg KOH/g, in some examples 30 mg KOH/g to 110 mg KOH/g, in some examples 50 mg KOH/g to 110 mg KOH/g, and a second polymer having acidic side groups that has an acidity of 110 mg KOH/g to 130 mg KOH/g.
  • the thermally activatable laminating material may comprise two different polymers having acidic side groups: a first polymer having acidic side groups that has a melt flow rate of about 10 g/10 minutes to about 50 g/10 minutes and an acidity of from 10 mg KOH/g to 110 mg KOH/g, in some examples 20 mg KOH/g to 110 mg KOH/g, in some examples 30 mg KOH/g to 110 mg KOH/g, in some examples 50 mg KOH/g to 110 mg KOH/g, and a second polymer having acidic side groups that has a melt flow rate of about 50 g/10 minutes to about 120 g/10 minutes and an acidity of 110 mg KOH/g to 130 mg KOH/g.
  • the first and second polymers may be absent of ester groups.
  • the ratio of the first polymer having acidic side groups to the second polymer having acidic side groups can be from about 10:1 to about 2:1.
  • the ratio can be from about 6:1 to about 3:1, in some examples about 4:1.
  • the thermally activatable laminating material may comprise a polymer having a melt viscosity of 15000 poise or less, in some examples a melt viscosity of 10000 poise or less, in some examples 1000 poise or less, in some examples 100 poise or less, in some examples 50 poise or less, in some examples 10 poise or less; said polymer may be a polymer having acidic side groups as described herein.
  • the resin may comprise a first polymer having a melt viscosity of 15000 poise or more, in some examples 20000 poise or more, in some examples 50000 poise or more, in some examples 70000 poise or more; and in some examples, the resin may comprise a second polymer having a melt viscosity less than the first polymer, in some examples a melt viscosity of 15000 poise or less, in some examples a melt viscosity of 10000 poise or less, in some examples 1000 poise or less, in some examples 100 poise or less, in some examples 50 poise or less, in some examples 10 poise or less.
  • the resin may comprise a first polymer having a melt viscosity of more than 60000 poise, in some examples from 60000 poise to 100000 poise, in some examples from 65000 poise to 85000 poise; a second polymer having a melt viscosity of from 15000 poise to 40000 poise, in some examples 20000 poise to 30000 poise, and a third polymer having a melt viscosity of 15000 poise or less, in some examples a melt viscosity of 10000 poise or less, in some examples 1000 poise or less, in some examples 100 poise or less, in some examples 50 poise or less, in some examples 10 poise or less; an example of the first polymer is Nucrel® 960 (from DuPont), and example of the second polymer is Nucrel® 699 (from DuPont), and an example of the third polymer is A-C® 5120 or A-C® 5180 (from Honeywell).
  • the first, second and third polymers may be polymers having acidic side groups as described herein.
  • the melt viscosity can be measured using a rheometer, e.g. a commercially available AR-2000 Rheometer from Thermal Analysis Instruments, using the geometry of: 25mm steel plate-standard steel parallel plate, and finding the plate over plate rheometry isotherm at 120°C, 0.01 Hz shear rate.
  • the thermally activatable laminating material comprises a single type of polymer
  • the polymer may have a melt viscosity of 6000 poise or more, in some examples a melt viscosity of 8000 poise or more, in some examples a melt viscosity of 10000 poise or more, in some examples a melt viscosity of 12000 poise or more.
  • the thermally activatable laminating material comprises a plurality of polymers all the polymers may together form a mixture that has a melt viscosity of 6000 poise or more, in some examples a melt viscosity of 8000 poise or more, in some examples a melt viscosity of 10000 poise or more, in some examples a melt viscosity of 12000 poise or more.
  • melt viscosity can be measured using standard techniques.
  • the melt viscosity can be measured using a rheometer, e.g. a commercially available AR-2000 Rheometer from Thermal Analysis Instruments, using the geometry of: 25mm steel plate-standard steel parallel plate, and finding the plate over plate rheometry isotherm at 120°C, 0.01 Hz shear rate.
  • the thermally activatable laminating material may comprise two different polymers having acidic side groups that are selected from co-polymers of ethylene and an ethylenically unsaturated acid of either acrylic acid or methacrylic acid; or ionomers thereof, such as methacrylic acid and ethylene-acrylic or methacrylic acid co-polymers which are at least partially neutralized with metal ions (e.g. Zn, Na, Li) such as Surlyn® ionomers.
  • metal ions e.g. Zn, Na, Li
  • the thermally activatable laminating material may comprise (i) a first polymer that is a copolymer of ethylene and an ethylenically unsaturated acid of either acrylic acid and methacrylic acid, wherein the ethylenically unsaturated acid of either acrylic or methacrylic acid constitutes from 8 wt% to about 16 wt% of the copolymer, in some examples 10 wt% to 16 wt% of the copolymer; and (ii) a second polymer that is a copolymer of ethylene and an ethylenically unsaturated acid of either acrylic acid and methacrylic acid, wherein the ethylenically unsaturated acid of either acrylic or methacrylic acid constitutes from 12 wt% to about 30 wt% of the copolymer, in some examples from 14 wt% to about 20 wt% of the co-polymer, in some examples from 16 wt% to about 20 wt% of the cop
  • the thermally activatable laminating material may comprise a polymer having acidic side groups, as described above (which may be free of ester side groups), and a polymer having ester side groups.
  • the polymer having ester side groups may be a thermoplastic polymer.
  • the polymer having ester side groups may further comprise acidic side groups.
  • the polymer having ester side groups may be a copolymer of a monomer having ester side groups and a monomer having acidic side groups.
  • the polymer may be a copolymer of a monomer having ester side groups, a monomer having acidic side groups, and a monomer absent of any acidic and ester side groups.
  • the monomer having ester side groups may be a monomer selected from esterified acrylic acid or esterified methacrylic acid.
  • the monomer having acidic side groups may be a monomer selected from acrylic or methacrylic acid.
  • the monomer absent of any acidic and ester side groups may be an alkylene monomer, including, but not limited to, ethylene or propylene.
  • the esterified acrylic acid or esterified methacrylic acid may, respectively, be an alkyl ester of acrylic acid or an alkyl ester of methacrylic acid.
  • the alkyl group in the alkyl ester of acrylic or methacrylic acid may be an alkyl group having 1 to 30 carbons, in some examples 1 to 20 carbons, in some examples 1 to 10 carbons, in some examples 1 to 5 carbons; in some examples selected from methyl, ethyl, iso-propyl, n-propyl, t-butyl, iso-butyl, n-butyl and pentyl.
  • the polymer having ester side groups may be a copolymer of a first monomer having ester side groups, a second monomer having acidic side groups and a third monomer which is an alkylene monomer absent of any acidic and ester side groups.
  • the polymer having ester side groups may be a copolymer of (i) a first monomer having ester side groups selected from esterified acrylic acid or esterified methacrylic acid, in some examples an alkyl ester of acrylic or methacrylic acid, (ii) a second monomer having acidic side groups selected from acrylic or methacrylic acid and (iii) a third monomer which is an alkylene monomer selected from ethylene and propylene.
  • the first monomer may constitute 1% to 50% by weight of the copolymer, in some examples 5% to 40% by weight, in some examples 5% to 20% by weight of the copolymer, in some examples 5% to 15% by weight of the co-polymer.
  • the second monomer may constitute 1% to 50 % by weight of the co-polymer, in some examples 5% to 40% by weight of the co-polymer, in some examples 5% to 20% by weight of the co-polymer, in some examples 5% to 15% by weight of the co-polymer.
  • the first monomer can constitute 5% to 40 % by weight of the co-polymer, the second monomer constitutes 5% to 40% by weight of the co-polymer, and with the third monomer constituting the remaining weight of the co-polymer. In some examples, the first monomer constitutes 5% to 15% by weight of the co-polymer, the second monomer constitutes 5% to 15% by weight of the co-polymer, with the third monomer constituting the remaining weight of the co-polymer. In some examples, the first monomer constitutes 8% to 12% by weight of the co-polymer, the second monomer constitutes 8% to 12% by weight of the co-polymer, with the third monomer constituting the remaining weight of the co-polymer.
  • the first monomer constitutes about 10% by weight of the co-polymer
  • the second monomer constitutes about 10% by weight of the co-polymer
  • with the third monomer constituting the remaining weight of the co-polymer.
  • the polymer may be selected from the Bynel® class of monomer, including Bynel® 2022 and Bynel® 2002, which are available from DuPont.
  • the polymer having ester side groups may have an acidity of 50 mg KOH/g or more, in some examples an acidity of 60 mg KOH/g or more, in some examples an acidity of 70 mg KOH/g or more, in some examples an acidity of 80 mg KOH/g or more.
  • the polymer having ester side groups may have an acidity of 100 mg KOH/g or less, in some examples 90 mg KOH/g or less.
  • the polymer having ester side groups may have an acidity of 60 mg KOH/g to 90 mg KOH/g, in some examples 70 mg KOH/g to 80 mg KOH/g.
  • the polymer having ester side groups may have a melt flow rate of about 10 g/10 minutes to about 120 g/10 minutes, in some examples about 10 g/10 minutes to about 50 g/10 minutes, in some examples about 20 g/10 minutes to about 40 g/10 minutes, in some examples about 25 g/10 minutes to about 35 g/10 minutes.
  • the polymer, polymers, copolymer or copolymers of the thermally activatable laminating material can in some examples be selected from the Nucrel® family of polymers (e.g. Nucrel® 403, Nucrel® 407, Nucrel® 609HS, Nucrel® 908HS, Nucrel® 1202HC, Nucrel® 30707, Nucrel® 1214, Nucrel® 903, Nucrel® 3990, Nucrel® 910, Nucrel® 925, Nucrel® 699, Nucrel® 599, Nucrel® 960, Nucrel® RX 76, Nucrel® 2806, Bynel® 2002, Bynel® 2014, Bynel® 2020 and Bynel® 2022 (sold by DuPont)), the AC family of polymers (e.g.
  • Escor 5020 7.5% (sold by Exxon Mobil), the TafmerTM family of polymers (e.g. TafmerTM MA9015 (sold by Mitsui)) and the Surlyn® family of polymers (e.g. Surlyn® 1652 (sold by DuPont)).
  • TafmerTM family of polymers e.g. TafmerTM MA9015 (sold by Mitsui)
  • Surlyn® family of polymers e.g. Surlyn® 1652 (sold by DuPont)
  • Described herein is a process for preparing a flexible packaging material comprising:
  • reference numeral “1” denotes a second flexible substrate
  • reference numeral “2” denotes a thermally activatable laminating material
  • reference numeral “3” denotes a first flexible substrate
  • reference numeral "4" denotes a primer comprising poly(acrylic acid) and/or poly(methacrylic acid)
  • reference numeral "5" denotes an ink composition
  • reference numeral "6” denotes a flexible packaging material.
  • Figure 1 depicts a process in which a second flexible substrate 1 is coated with a thermally activatable laminating material 2, in a deposition process.
  • the thermally activatable laminating material 2 is then contacted with a first surface of a first flexible substrate 3 comprising a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) 4 and an ink composition 5 in a thermal laminating step to form a flexible packaging material 6.
  • a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) 4
  • an ink composition 5 in a thermal laminating step
  • a process for preparing a flexible packaging material comprises a step of printing an ink composition onto a first surface of a first flexible substrate coated with a primer comprising poly(acrylic acid) and/or poly(methacrylic acid), or providing a first flexible substrate comprising a first surface coated with a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) and an ink composition printed onto the first surface of the first flexible substrate.
  • the first flexible substrate is a first flexible substrate as described herein previously.
  • the ink composition used in the process is an ink composition as described herein previously.
  • the ink composition may be printed onto the first surface of the first flexible substrate in a conventional electrophotographic or electrostatic printing process using a conventional electrophotographic or electrostatic printing apparatus. Examples of suitable electrophotographic or electrostatic printing equipment are the HP Indigo digital presses.
  • the first flexible substrate comprises a transparent material and the ink composition is printed onto the first surface of the first flexible substrate thereof in a reverse printing process such that the printed image or information appears correct when viewed through the flexible substrate.
  • the reverse printing process and thermally laminating the printed surface of the first flexible substrate to the second flexible substrate (as described below), the printed image or information is viewed correctly in the final product and is protected from damage by the first flexible substrate which forms the outermost layer of the packaging material.
  • the first flexible substrate comprising the printed image or information can be wound onto a roll or spool and stored until the laminating step is carried out, if required.
  • a process for preparing a flexible packaging material comprises a step of extruding a thermally activatable laminating material onto a first surface of a first flexible substrate coated with a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) to form a thermally activatable laminating material disposed on the first surface of the first flexible substrate, or providing a second flexible substrate with a thermally activatable laminating material extruded onto the first surface of the second flexible substrate.
  • extrusion is to be understood as meaning melting the thermally activatable laminating material and passing it through an extrusion die onto a base layer material in such a manner that the materials form a structure, for example a film, of defined layers of different materials.
  • extrusion die onto a base layer material in such a manner that the materials form a structure, for example a film, of defined layers of different materials.
  • the second flexible substrate is a second flexible substrate as described previously.
  • the base material or the base layer is a preformed base layer.
  • the thermally activatable laminating material is a thermally activatable laminating material as described previously.
  • the step of extrusion of the thermally activatable laminating substrate onto the surface of the second flexible substrate to form a layered structure can be performed using any apparatus suited to extrusion processes in which one material is extruded onto a base layer to form layered films.
  • Such machinery is known in the art.
  • each component of the thermally activatable laminating material may be melt blended and then extruded to form pellets of blended thermally activatable laminating material. These pellets may then be used in the extrusion step to form a thermally activatable laminating material disposed on the second flexible substrate.
  • the thermally activatable laminating material may comprise a blend of materials, the blend being achieved by dry blending pellets of each component and adding the mixture of pellets to the extruding machine used to extrude the thermally activatable laminating material and form the layered structure of a thermally activatable laminating material disposed on the second flexible substrate.
  • the process may further comprise deposition of a sealant material to form a sealant layer disposed on a surface of the second flexible substrate other than the surface on which the thermally activatable laminating material is disposed.
  • the material used to form the sealant layer may be as described previously.
  • the step of depositing the sealant material onto the second flexible substrate may occur before or after the step of extruding the thermally activatable laminating material.
  • the step of depositing the sealant layer may take place by any suitable process, for example, extrusion coating, flexo coating, gravure or screen printing.
  • the steps of extruding a thermally activatable laminating material and depositing a sealant layer result in a multi-layer or trilayer material being obtained in which the second flexible substrate has a thermally activatable laminating material disposed on a first surface and a sealant layer disposed on a surface other than the first surface.
  • the second flexible substrate and sealant layer are pre-formed as a functional substrate.
  • a process for preparing a flexible packaging material comprises a step of contacting under conditions of temperature greater or equal to 50°C the thermally activatable laminating material with the first surface of the first flexible substrate coated with a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) and comprising the ink composition.
  • This step may be referred to as a laminating step or a thermal laminating step.
  • the result of this step is a thermally laminated flexible packaging material, which, as mentioned previously, comprises the first flexible substrate as the intended outermost layer of the packaging in use, thus protecting from damage the printed image or information formed by the ink composition.
  • the first flexible substrate coated with a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) and comprising the printed image or information is brought into a particular alignment with the second flexible substrate comprising the thermally activatable laminating material before being subjected to the thermal laminating step.
  • the step of contacting under conditions of temperature greater or equal to 50°C the thermally activatable laminating material with the first surface of the first flexible substrate comprising the printed ink composition produces the flexible packaging material which is ready for use immediately upon cooling to room temperature, even when using thickener materials.
  • the processes for preparing a flexible packaging material described herein require no additional curing time, or stated differently, zero curing time.
  • the presently described processes are therefore advantageous over existing methods for producing flexible packaging materials containing LEP printed images or information in which laminating adhesives are used.
  • Such laminating adhesives, both "solvent-based” and “solvent-free” adhesives require curing times of at least several days, thus removing the advantage of speed that digital printing can offer.
  • the presently described processes are also advantageous over existing methods for producing flexible packaging materialssuch as zero cure time pouches for sterilization, hot fill, pasteurization and retort.
  • a process for preparing a flexible packaging material comprises a step of contacting under conditions of temperature greater or equal to 50°C the thermally activatable laminating material of the second flexible substrate with the first surface of the first flexible substrate and comprising the printed ink composition, and a step of cooling the resulted material to room temperature, thereby obtaining a ready-to-use flexible packaging material.
  • the laminating step may be carried out on any apparatus suited for performing such a task. Suitable laminating equipment for preparing flexible packaging comprising laminated materials is known in the art.
  • the laminating apparatus on which the thermal laminating step may be carried out may comprise pre-heating rolls, heating or nip rolls, and chill or cooling rolls through which the thermally laminated multilayer material passes, to further speed up the cooling process.
  • the laminating step carried out on the nip roll may be carried out at a temperature greater or equal to 50°C to partially melt the thermally activatable laminating material and/or the polymer resin of the ink composition printed on the first flexible substrate at the laminating nip, and thereby creating a bond between the materials.
  • the temperature for the laminating nip or step may be less than about 180°C, for example less than about 170°C, for example less than about 160°C, for example less than about 150°C, for example less than about 140°C, for example less than about 130°C, for example less than about 120°C, for example less than about 110°C, for example less than about 100°C, for example less than about 90°C, for example less than about 80°C, for example less than about 70°C, for example less than about 60°C.
  • the temperature for the laminating nip or step may be greater than about 50°C, for example greater than about 60°C, for example greater than about 70°C, for example greater than about 80°C, for example greater than about 90°C, for example greater than about 100°C, for example greater than about 110°C, for example greater than about 120°C, for example greater than about 130°C, for example greater than about 140°C, for example greater than about 150°C, for example greater than about 160°C, for example greater than about 170°C.
  • the temperature for the laminating nip is of 50-180°C. It will be understood that the temperature required for efficient thermal lamination will depend on the nature or composition of the thermally activatable laminating material and/or the polymer resin of the ink composition and the associated melting temperatures.
  • the surface of the first flexible substrate printed with the ink composition is contacted with the surface of the second flexible substrate on which a thermally activatable laminating material is disposed for a period of 100-600 ms.
  • the pressure for the laminating nip or step may be less than about 10 bar, for example less than about 9 bar, for example less than about 8 bar, for example less than about 7 bar, for example less than about 6 bar, for example less than about 5 bar, for example less than about 4 bar, for example less than about 3 bar, for example about 2 bar.
  • the pressure for the laminating nip or step may be greater than about 2 bar, for example greater than about 3 bar, for example greater than about 4 bar, for example greater than about 5 bar, for example greater than about 6 bar, for example greater than about 7 bar, for example greater than about 8 bar, for example greater than about 9 bar, for example about 10 bar. It will be understood that the pressure required for efficient thermal lamination will depend on the nature or composition of the thermally activatable laminating material and the associated melting temperature.
  • Adhesive for pre-lamination of second flexible substrate Dow Adcote 811 + catalyst F-9.
  • Lamination of materials to form the second flexible substrate Apparatus: UTECO MISTRAL [1260 mm width] Coating/Laminating machine Table 1: Parameters for lamination of materials to form the second flexible substrate Parameter Value Unwinder A tension (N) 6 Unwinder B tension (N) 10 Rewinder Tension (N) 23 Nip temperature (°C) 60 Nip pressure (bar) 4 Lamination speed (m/min) 40 Corona A (W) 0 Corona B (W) 2000 Room temperature (°C) 15-35 Room humidity (%) 30-80 Dr blade pressure (bar) 4 Gravure type 60-70 Oven 1 Temperature (°C) 70 Oven 2 Temperature (°C) 85 Oven 3 Temperature (°C) 100 Adhesive coat weight (gsm) 3.5
  • Extrusion coating of Thermally Activatable Laminating Material (TALM): Apparatus: Coex Extrusion laminator & Coater MODEL EXCOL1 - 12/35 from Dolci Extrusion SRL
  • the prelaminate Al (7 ⁇ m) / ADH / BOPA (15 ⁇ m) / ADH / cPP (80 ⁇ m) was loaded onto the main unwinder, and the thermally activatable laminating material was loaded into the extruder, and the apparatus operated according to the parameters set out in Table 2: Table 2 Parameter Value Unwinder A tension (N) 11 Unwinder B tension (N) 9 Rewinder Tension (N) 28 Chill roll temperature (°C) 60 Corona Tr (W) 2000 Die temperature (°C) 275 Die height (mm) 230 Extruder A temperature (°C) 270 RPM (A,B,C) 66 Die pressure (bar) 140 Nip pressure (bar) 5 Pressure roll temperature (°C) 120 Lamination speed (m/min) 240 Corona Rewinder (W) 4500
  • the result of the above processes is a prelaminate of thermally activatable laminating material as a top layer of a multilayer material in the form TALM (10 ⁇ m) / Al (7 ⁇ m) / ADH / BOPA (15 ⁇ m) / ADH / cPP (80 ⁇ m).
  • This laminate is further laminated to a printed first flexible substrate PET / primer comprising poly(acrylic acid) and/or poly(methacrylic acid) / ink composition as described below.
  • a first flexible substrate coated with a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) on a surface of the first flexible substrate to which an ink composition was printed was used: the Sarafil® DP100-1G and Sarafil® DB100-1GO products (available from Polyplex).
  • An image was electrostatically printed using a HP Indigo 20000 printing press and ElectroInk® 4.5 (available from HP Indigo), a liquid electrophotographic ink composition comprising a thermoplastic resin comprising ethylene acrylic acid, ethylene methacrylic acid copolymers, on the PET film, the image included white and non-printed areas, the printed areas having an ink coverage of 100-350% (1.0gsm-4.0gsm coat weight of the thermoplastic resin on the PET film).
  • Table 3 Print substrate definitions PET BOPP Type Film Film Material PET BOPP Face-stock Transparent Transparent Gloss level Semi-matte Semi-matte Second transfer (kg) 250 250 Blanket temperature (°C) 105 105 Feed Fan (V) 8 8 PTH (°C) Off Off Thickness ( ⁇ m) 12 20
  • the printed first flexible substrate coated with a primer comprising poly(acrylic acid) and/or poly(methacrylic acid) is thermally laminated to the second flexible substrate on which the thermally activatable laminating material is deposited.
  • the laminate performance was verified at zero cure time by measuring the lamination bond strength immediately after the flexible packaging material had been cooled at room temperature.
  • Lamination bond strength was measured according to ASTM F0904-98R08.
  • the resistivity of the flexible packaging material at a temperature below 0°C was also verified.
  • the deep freeze test was done by preparing 200 x 100 mm package from the laminate. The package was manufactured from the flexible packaging material as follows:
  • Hot fill is a sterilization process that is used for many applications.
  • hot fill test was done by preparing 200 x 100 mm package from the laminate. The package was manufactured from the flexible packaging material as follows:
  • Hot fill and pasteurization is a sterilization process that is used for many applications.
  • pasteurization test was done by preparing 200 x 100 mm package from the laminate. The package was manufactured from the flexible packaging material as follows:
  • Retort is one of the most complicated flexible packaging processes since the whole package is heated to elevated temperature with steam and then cooled back to room temperature under pressure. Retort cannot be met with some existing flexible packaging materials due to primers used having unsuitable water resistance and lamination bond strength values being insufficient.
  • retort test was done by preparing 200 x 100 mm package from the laminate. The package was manufactured from the flexible packaging material as follows:
  • the package was then removed from the autoclave and visually inspected for detection of:

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Laminated Bodies (AREA)

Claims (14)

  1. Vorgang zum Herstellen eines flexiblen Verpackungsmaterials, Folgendes umfassend:
    - Bereitstellen eines ersten flexiblen Substrats, das mit einem Primer beschichtet ist, welcher Poly(acrylsäure) und/oder Poly(methacrylsäure) enthält;
    - Drucken einer flüssigen elektrofotografischen Drucktintenzusammensetzung auf die Oberfläche des ersten flexiblen Substrats;
    - Extrudieren eines thermisch aktivierbaren Laminiermaterials auf eine Oberfläche eines zweiten flexiblen Substrats; und
    - Kontaktieren der Oberfläche des zweiten flexiblen Substrats, auf die das thermisch aktivierbare Laminiermaterial abgeschieden ist, mit der Oberfläche des ersten flexiblen Substrats, das mit der flüssigen elektrofotografischen Drucktintenzusammensetzung bedruckt ist, bei Temperaturen von mehr als oder gleich 50°C.
  2. Verfahren nach Anspruch 1, wobei das erste flexible Substrat ein Material eines biaxial orientierten Polyethylenterephthalats (BOPET), eines biaxial orientierten Polypropylens (BOPP) oder eines biaxial orientierten Polyamids (BOPA) aufweist.
  3. Verfahren nach Anspruch 1, wobei der Primer Poly(acrylsäure) aufweist.
  4. Verfahren nach Anspruch 1, wobei die Tintenzusammensetzung ein Copolymer aus einem Alkylenmonomer und einem Monomer, das aus Acrylsäure und Methacrylsäure ausgewählt ist, aufweist.
  5. Verfahren nach Anspruch 1, wobei das zweite flexible Substrat einen Film oder ein Blatt Papier, eine metallische Folie und/oder ein Kunststoffmaterial aufweist.
  6. Verfahren nach Anspruch 1, wobei das thermisch aktivierbare Laminiermaterial ein Copolymer aus einem Alkylenmonomer und einem Monomer, das aus Acrylsäure und Methacrylsäure ausgewählt ist, aufweist.
  7. Verfahren nach Anspruch 1, ferner umfassend ein Dichtungsmaterial auf dem zweiten flexiblen Substrat, zum Bilden einer Dichtungsschicht, die auf eine Oberfläche des zweiten flexiblen Substrats aufgebracht ist, die nicht die Oberfläche ist, auf die das thermisch aktivierbare Laminiermaterial aufgebracht ist.
  8. Verfahren nach Anspruch 1, wobei die Oberfläche des ersten flexiblen Substrats, das mit der Tintenzusammensetzung bedruckt ist, mit der Oberfläche des zweiten flexiblen Substrats, auf die das thermisch aktivierbare Laminiermaterial aufgebracht ist, bei einer Temperatur von 50-180°C in Kontakt gebracht wird.
  9. Verfahren nach Anspruch 1, wobei die Oberfläche des ersten flexiblen Substrats, das mit der Tintenzusammensetzung bedruckt ist, mit der Oberfläche des zweiten flexiblen Substrats, auf die das thermisch aktivierbare Laminiermaterial aufgebracht ist, für einen Zeitraum von 100-600 ms in Kontakt gebracht wird.
  10. Verfahren nach Anspruch 1, ferner umfassend das Kühlen des Materials, das aus dem Verfahrensschritt des Inkontaktbringens der Oberfläche des ersten flexiblen Substrats, die mit der Tintenzusammensetzung bedruckt ist, mit der Oberfläche des zweiten flexiblen Substrats erhalten wurde, auf die das thermisch aktivierbare Laminiermaterial abgeschieden ist, wodurch das flexible Verpackungsmaterial hergestellt wird.
  11. Flexibles Verpackungsmaterial, Folgendes umfassend:
    - ein erstes flexibles Substrat, das mit einem Primer beschichtet ist, der Poly(acrylsäure) und/oder Poly(methacrylsäure) enthält;
    - eine bedruckte flüssige elektrofotografische Drucktintenzusammensetzung, die auf eine Oberfläche des ersten flexiblen Substrats aufgebracht ist; und
    - ein zweites flexibles Substrat, auf das ein thermisch aktivierbares Laminiermaterial abgeschieden ist, wobei die Oberfläche des zweiten flexiblen Substrats, auf das ein thermisch aktivierbares Laminiermaterial abgeschieden ist, thermisch auf die Oberfläche des ersten flexiblen Substrats laminiert wird, die mit der Tintenzusammensetzung bedruckt ist.
  12. Flexibles Verpackungsmaterial nach Anspruch 11, wobei das erste flexible Substrat ein Material eines biaxial orientierten Polyethylenterephthalats (BOPET), eines biaxial orientierten Polypropylens (BOPP) oder eines biaxial orientierten Polyamids (BOPA) aufweist
  13. Flexible Verpackung, umfassend ein flexibles Material nach Anspruch 11.
  14. Flexible Verpackung nach Anspruch 13, wobei das erste flexible Substrat ein Material eines biaxial orientierten Polyethylenterephthalats (BOPET), eines biaxial orientierten Polypropylens (BOPP) oder eines biaxial orientierten Polyamids (BOPA) aufweist
EP16750699.7A 2016-07-29 2016-07-29 Matériau d'emballage flexible et son procédé de préparation Active EP3414092B1 (de)

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US20190193380A1 (en) 2019-06-27
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CN109070574A (zh) 2018-12-21
US11141962B2 (en) 2021-10-12

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